Vat dyes of the anthraquinone 1, 3, 4-oxdiazole series



Patented June 13, 1950 i I UNITED STATES PATENT OFFICE VAT DYES OF THE ANTHRAQUINONE 1,3,4-OXDIAZOLE SERIES Frederic B. Stilmar, Wilmington, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, iDeL, a. corporation of Delaware N Drawing. Application March 15, 1949, Serial No. 81,620

1 Claim. (01. 260 307.'5)

This invention relates to the preparation of a The nitro groups in the l-positionon the anthranew red vat dye of the anthraquinone series, quinone nuclei are then converted to amino and more particularly to a bis-anthraquinoneroups by reacting the nitro compound with cxdiazole. ammonia.

A continuous effort has been made for a numg, The following examples are given to illustrate ber of years to produce in the anthraquinone the invention. The parts used are by weight, vat dye series a red dye which would dye in unless otherwise specified. bright red shades and have the excellent fastness properties characteristic in general of the Example 1 anthraquinone vat dyes. While several red dyes lo v e have been produced in the anthraquinone series, g jg gifi fifg$25322 21 5 those so far available commercially either 350 parts of orthodich-lorobenzene are heated to lacking in strength or brightness or in their fast- C for 2 hours The mass is filtered at 100 ness properties such as fastness to light, bleach, C d the resultiilg filter cake is Washed with launqermg n benzene. The oxalyl-bis(l-nitroanthraquinone- It IS an ObJest 01 h present mvenplon to j 2-carbony1 hydrazine) is obtained in the form duce a red vat dye in the anthraqumone series of colorless plates having a melting point of which dyes in strong and relatively bright red O o shades and Which shows good general fastness 313 315 It has the formula" properties. A more particular object of the in- N01 vention is to produce a red dyestuff of the anthra- (B (j: 5 quinone series having very desirable dyeing and g g H fastness properties, which has the general for- 0 o mula:

- o N112 NHa o I NN N--N '5 Li, ll By using l-aminoanthraquinone 2 carbonyl hydrazine and oxalyl chloride in the above example, there is obtained the corresponding di- H g amino compound of the formula: 0

NE: E

H NE NE 0 6 l I Example 2 l l Fifteen (15) parts of oxalyl bis-(l-nitroanthraquinone-Z-carbonyl hydrazine), obtained as in g Example 1, parts of thionyl chloride, and 250 whic i turn, is i closed b means of acid benzene and dried. The bis-(l-nitroanthraqui- 0 NO: 0 N02 0 NH 0 NHNH NHN The new vat dye of this invent1on may be pre- 5 A A g pared by reacting 1-nitroanthraquinone-2-car- A g g g bonyl hydrazine with oxalyl chloride to produce 85 the bis-hydrazide of the formula:

II 0 N02 0 A l 1 parts of nitrobenzene are heated at 165-170 C. for 6 hours. The mass is filtered, washed with Condensing agents to the bis'oxdiazole of the none oxdiazole) thus obtained is in the form of formula; yellowish chunky crystals. It has the formula:

No, 0 N0, 0 N-N N-N N-N N-N 4% M 15 t at t Example 3 Five (5) parts of the product of Example 2 are suspended in 350 parts of nitrobenzene. Ammonia is passed through the reaction mixture at 170-180 C. for 2 hours. The resulting product, which consists of long bluish-red crystals, is filtered off, washed with benzene and dried. It has the formula:

0 NH2 NH: O

This bis-(1 aminoanthraqujnone oxdiazole) dissolves in sulfuric acid with a weak yellow color and dyes cotton in strong bluish-red shades from a violet alkaline hydrosulfite vat. It shows good fastness to light, bleach and washing when tested by the usual standard tests.

The reaction of the anthraquinone-Z-carbonyl hydrazine with the oxalyl chloride may be carried out in any inert solvent such as nitrobenzene, trichlorobenzene, etc., at temperatures of from 150 to 200 C. The thionyl chloride used in the above examples to effect ring closure of the hydrazide to the oxdiazole may be replaced by other acid condensing agents such as phosphorus oxychloride, p-toluene sulfonic acid or the like. The ring closure of the hydrazides to the oxdi'azoles is preferably efiected at temperatures of to 210 C. This ring closure may be carried out in any of the usual inert organic s01 vents such as aromatic hydrocarbons and their nitrated and chlorinated derivatives. When desired, the ring closure reaction may be carried out without isolation of the hydrazide from the or ganic reaction medium in which it is formed.-

I claim:

The bis-(1-aminoanthraquinoneoxdiazole) of the formula:

0 NE: NH; O

FREDERIC B. STILMAR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Stilmar Mar. 22, 1949 Number 

